Process of making camphene.



' acids as solvents,

UNITED STATES PATENT OFFICE.

AUGUSTUS BISOHLER. AND ANTON BASELLI, OF BASEL, SWITZERLAND, ASSIGNORS,BY MESNE ASSIGNMENTS, TO I. BASLER &

GIE., OF BASE'L, SWITZERLAND, A FIRM.

PROCESS MAKING CAMPHENE.

T 0 all whom it may concern:

Be it known that we, AUGUSTUS BISCH- LER, doctor of philosophy andchemist, a subjectof the Emperor of Russia, and resident of Basel,Switzerland, and ANTON BASELLI, doctor of philosophy and chemist, asubject of the Emperor of Austria-Hungary, and resident of Basel,Switzerland, have invented a new and useful Process for the Manufactureof Camphene, of which the following is a full, clear, and exactspecification.

The present invention relates to the manufacture of camphene used forthe manufacture of camphor. One of the oldest methods for obtainingcamphene free from chlorin consists in heating pinene hydrochlorid witha large excess of powdered sodium stearate or benzoate for 40 hours at200.C. The chief objections to this process are the large excess of soapand the prolonged heating.

The process described in the British specification No. 26618 of 1901,namely heating pinene hydrochlorid with bases in aqueous solution as forinstance soda 1 e or potash lye, in presence of alkali salts 0 higherfatty for 20 hours at 210220 Q. iln an autoclave, is said to be moreeconomica The alkali salts of higher fatty acids do not melt easily whenthey are anhydrous. On the other hand numerous salts of higher fattyacids are known, which melt easily even when anhydrous. By higher fattyacids we mean palmitic, 'stearic and oleic acids, and as an example ofthe easily melted salts just referred to, we would refer to salts ofeither of these acids with heavy metals.

According to the present invention inene hydrochlorid is heated with aneasily usible anhydrous metal salt of a higher fatty acid for some hoursat about 200 C. It is thus converted into camphene without using anautoclave and in a considerably shorter time than is possible accordingto either of the aforesaid processes.

As suitable easily fusible salts of higher fatty acids, may be named theco per salts, manganese salts, lead salts an. mercury salts.

In order that theoperation may be conducted in a vessel withoutpressure, the vessel is provided with a column which serves as a refluxcondenser and is so-large that the temperature within the mass in whichthe Specification of Letters Patent. Application filed September 131906. Serial No; 334.870.

Patented Jan. 7, 1908.

reaction is proceeding can riseto 200 C. A part of the camphene maydistil during the process, but the bulk of it is distilled in steam whenthe reaction is at an end.

Example I: 75 parts (I litharge are dissolved with aid of heat in 200parts of stearic acid and the heating is continued until the salt isanhydrous. Into this lead stearate 100 parts ofpinene hydrochlorid areintroduced and the solution is heated to 195 200 C. for 4 hours in avessel having a column as a reflux condenser. Lead stearochloridseparates at first and gradually reacts with the pinene hydrochloridwith formation of lead chlorid. The mass is allowed to cool to about 140C. and the camphene is distilled in steam. The stearic acid isregenerated and is used again in the process. The reaction is analogouswhen lead oleate is used, but in this case lead oleochlorid does notseparate, but only lead chlorid. Lead palmitate behaves similarly. It isnot necessary, however, to use the said acids in the pure state; amixture of acids such as is obtained by saponifying oils or fats may beused.

Example 11 A mlxture ofoleic and stearic acids, which may also containpalmitic acid, is converted into 00 per salts in the known manner bymeans of the calculated proportion of freshly precipitated coppercarbonate or cupric oxids. 300 parts of the dried copper salts areheated for some 5 hours at 195- 200 C. with 100 parts of pinenehydrochlorid. From time to time a sample of the oil condensed in thereflux condenser is removed and tested to see if it is free fromchlorin. The cam hene is distilled in steam and the fatty aci srecovered. When the fatty acid salt is not so easily melted as thosementioned in the previous examples, a substance which will aid theliquefaction, such as diethylanilin, may be added.

Example III: Manganese oleate is made by adding manganese sulfate toanoleic acid soa 240 parts of this oleate are heated with 100 parts ofinene hydrochlorid and 100 arts of diet iylanilin at 195200 C. for 8hours. When the reaction is complete the mixture is distilled in steamand the diethylanilin separated from the camphene in the distillate byaddition of acid.

What we'claim is:

1. The described process for the manufacture of camphene consisting ofheating piene hydrochlorid with an easily fusible, anhydrous metal saltof a higher fatty acid, and distilling the mixture of the reaction insteam in order to separate the camphene.

2. The described process for the manufacture of camphene consisting ofheating pinene hydrochlorid with an easily fusible anhydrous metal saltof a higher fatty acid for some hours at about 200 C. and distilling themixture of the reaction in steam in order to separate the camphene.

3. The described process for the manufacture of camphene consisting ofheating pinene hydrochlorid with an easily fusible anhydrous metal saltof a higher-fatty acid for some hours at about 200 C. in a vesselprovided 'With a column serving as a reflux condenser and distilling themixture of the reaction in steam in order to separate the camphene. A

4 The described process for the manufacture of camphene consisting ofheating pinene hydrochlorid with an easily fusible, anhydrous metal saltof a higher fatty acid in presence of diethylanilin at about 200 C.distilling the mixture of the reaction in steam, in order to separatefrom it the camphene and the diethylanilin and finally adding an acid tothe distillate in order to separate the camphene from the diethylanilin.

In witness whereof We have hereunto signed our names this 1st day ofSeptember,

AUGUSTUS BISCHLER. ANTON BASELLI.

Witnesses GEO. GIFFORD. AMAND BITTER.

